CN1795153B - Metallic compound fixed to a support, method for production and use of said compound in hydrocarbon metathesis reactions - Google Patents
Metallic compound fixed to a support, method for production and use of said compound in hydrocarbon metathesis reactions Download PDFInfo
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- CN1795153B CN1795153B CN2004800145147A CN200480014514A CN1795153B CN 1795153 B CN1795153 B CN 1795153B CN 2004800145147 A CN2004800145147 A CN 2004800145147A CN 200480014514 A CN200480014514 A CN 200480014514A CN 1795153 B CN1795153 B CN 1795153B
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- Prior art keywords
- compound
- aluminum oxide
- tungsten
- carrier
- hydrocarbon
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 82
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 61
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 45
- 239000004215 Carbon black (E152) Substances 0.000 title claims abstract description 44
- 238000005649 metathesis reaction Methods 0.000 title claims abstract description 25
- 229910000765 intermetallic Inorganic materials 0.000 title claims description 10
- 238000004519 manufacturing process Methods 0.000 title description 4
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 89
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 72
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 69
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 62
- 238000006243 chemical reaction Methods 0.000 claims abstract description 50
- 239000010937 tungsten Substances 0.000 claims abstract description 35
- 150000001335 aliphatic alkanes Chemical class 0.000 claims abstract description 19
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 16
- 239000000203 mixture Substances 0.000 claims abstract description 14
- 230000003647 oxidation Effects 0.000 claims abstract description 11
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 11
- 125000000217 alkyl group Chemical group 0.000 claims description 47
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical group CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 26
- 239000001294 propane Substances 0.000 claims description 13
- 230000000536 complexating effect Effects 0.000 claims description 8
- 230000004048 modification Effects 0.000 claims description 6
- 238000012986 modification Methods 0.000 claims description 6
- 239000003446 ligand Substances 0.000 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 3
- 239000002243 precursor Substances 0.000 abstract description 37
- 230000000737 periodic effect Effects 0.000 abstract description 7
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 239000006185 dispersion Substances 0.000 abstract description 6
- 150000002736 metal compounds Chemical class 0.000 abstract description 6
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 239000003054 catalyst Substances 0.000 abstract description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 abstract description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 abstract description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 2
- 239000005864 Sulphur Substances 0.000 abstract description 2
- 239000000460 chlorine Substances 0.000 abstract description 2
- 229910052801 chlorine Inorganic materials 0.000 abstract description 2
- 239000011737 fluorine Substances 0.000 abstract description 2
- 229910052731 fluorine Inorganic materials 0.000 abstract description 2
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 2
- 239000011574 phosphorus Substances 0.000 abstract description 2
- 238000003776 cleavage reaction Methods 0.000 abstract 1
- 238000005984 hydrogenation reaction Methods 0.000 abstract 1
- 230000006798 recombination Effects 0.000 abstract 1
- 238000005215 recombination Methods 0.000 abstract 1
- 230000007017 scission Effects 0.000 abstract 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 45
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 44
- 238000000034 method Methods 0.000 description 34
- -1 21 to 29 Chemical class 0.000 description 30
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 26
- 239000000377 silicon dioxide Substances 0.000 description 22
- 229910052739 hydrogen Inorganic materials 0.000 description 21
- 235000012239 silicon dioxide Nutrition 0.000 description 21
- 229960001866 silicon dioxide Drugs 0.000 description 21
- 239000001257 hydrogen Substances 0.000 description 20
- 239000007787 solid Substances 0.000 description 20
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 18
- 238000010521 absorption reaction Methods 0.000 description 18
- 125000001931 aliphatic group Chemical group 0.000 description 15
- 238000002360 preparation method Methods 0.000 description 15
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical class [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 14
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 14
- 238000002329 infrared spectrum Methods 0.000 description 14
- 229910052786 argon Inorganic materials 0.000 description 13
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical class [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 12
- 125000001118 alkylidene group Chemical group 0.000 description 11
- 229910052782 aluminium Inorganic materials 0.000 description 11
- 229910052799 carbon Inorganic materials 0.000 description 10
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 9
- 238000007327 hydrogenolysis reaction Methods 0.000 description 9
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 9
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 8
- 125000000753 cycloalkyl group Chemical group 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 229910052715 tantalum Inorganic materials 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 7
- 239000004411 aluminium Substances 0.000 description 7
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 7
- 239000012298 atmosphere Substances 0.000 description 7
- 238000002474 experimental method Methods 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 239000011521 glass Substances 0.000 description 7
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 7
- 238000012545 processing Methods 0.000 description 7
- MEOSMFUUJVIIKB-UHFFFAOYSA-N [W].[C] Chemical compound [W].[C] MEOSMFUUJVIIKB-UHFFFAOYSA-N 0.000 description 6
- 230000004913 activation Effects 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 229910052596 spinel Inorganic materials 0.000 description 6
- 239000011029 spinel Substances 0.000 description 6
- 229910052723 transition metal Inorganic materials 0.000 description 6
- 150000003624 transition metals Chemical class 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical compound [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 5
- 150000004645 aluminates Chemical class 0.000 description 5
- 159000000013 aluminium salts Chemical class 0.000 description 5
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 5
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 5
- 238000001354 calcination Methods 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 238000000859 sublimation Methods 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 4
- 150000001336 alkenes Chemical class 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 150000001721 carbon Chemical group 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000005906 dihydroxylation reaction Methods 0.000 description 4
- 238000007598 dipping method Methods 0.000 description 4
- 229910001679 gibbsite Inorganic materials 0.000 description 4
- 229910052987 metal hydride Inorganic materials 0.000 description 4
- 150000004681 metal hydrides Chemical class 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 230000002829 reductive effect Effects 0.000 description 4
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 3
- 229910003923 SiC 4 Inorganic materials 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 3
- 150000001345 alkine derivatives Chemical class 0.000 description 3
- 125000000304 alkynyl group Chemical group 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 229910001593 boehmite Inorganic materials 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 229910052805 deuterium Inorganic materials 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 239000001307 helium Substances 0.000 description 3
- 229910052734 helium Inorganic materials 0.000 description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 3
- 150000004678 hydrides Chemical class 0.000 description 3
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000003345 natural gas Substances 0.000 description 3
- 150000002902 organometallic compounds Chemical class 0.000 description 3
- 125000002524 organometallic group Chemical group 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- KQEIJFWAXDQUPR-UHFFFAOYSA-N 2,4-diaminophenol;hydron;dichloride Chemical compound Cl.Cl.NC1=CC=C(O)C(N)=C1 KQEIJFWAXDQUPR-UHFFFAOYSA-N 0.000 description 2
- 229910018516 Al—O Inorganic materials 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 229910052728 basic metal Inorganic materials 0.000 description 2
- 150000003818 basic metals Chemical class 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 235000011089 carbon dioxide Nutrition 0.000 description 2
- 230000008859 change Effects 0.000 description 2
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- 239000003245 coal Substances 0.000 description 2
- 230000000994 depressogenic effect Effects 0.000 description 2
- 229910001648 diaspore Inorganic materials 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- 238000007323 disproportionation reaction Methods 0.000 description 2
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- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
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- 239000012535 impurity Substances 0.000 description 2
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- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 2
- 229910052747 lanthanoid Inorganic materials 0.000 description 2
- 150000002602 lanthanoids Chemical class 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
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- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 2
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- 108091071338 17 family Proteins 0.000 description 1
- 229910002016 Aerosil® 200 Inorganic materials 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910002515 CoAl Inorganic materials 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 229910015372 FeAl Inorganic materials 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- 229910010093 LiAlO Inorganic materials 0.000 description 1
- 229910020068 MgAl Inorganic materials 0.000 description 1
- 229910016583 MnAl Inorganic materials 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- QVRYCILXIXLVCU-UHFFFAOYSA-N N.[AlH3] Chemical compound N.[AlH3] QVRYCILXIXLVCU-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229920002367 Polyisobutene Polymers 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229910018557 Si O Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
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- 150000001255 actinides Chemical class 0.000 description 1
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- 230000032683 aging Effects 0.000 description 1
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- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
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- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 1
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- XFWJKVMFIVXPKK-UHFFFAOYSA-N calcium;oxido(oxo)alumane Chemical compound [Ca+2].[O-][Al]=O.[O-][Al]=O XFWJKVMFIVXPKK-UHFFFAOYSA-N 0.000 description 1
- FQNHWXHRAUXLFU-UHFFFAOYSA-N carbon monoxide;tungsten Chemical group [W].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-] FQNHWXHRAUXLFU-UHFFFAOYSA-N 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
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- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
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- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 1
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- 125000000219 ethylidene group Chemical group [H]C(=[*])C([H])([H])[H] 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 239000010433 feldspar Substances 0.000 description 1
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- 229910052733 gallium Inorganic materials 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
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- 150000002431 hydrogen Chemical class 0.000 description 1
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- YQNQTEBHHUSESQ-UHFFFAOYSA-N lithium aluminate Chemical compound [Li+].[O-][Al]=O YQNQTEBHHUSESQ-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
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- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 1
- 238000006140 methanolysis reaction Methods 0.000 description 1
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- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920003251 poly(α-methylstyrene) Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- OSFBJERFMQCEQY-UHFFFAOYSA-N propylidene Chemical group [CH]CC OSFBJERFMQCEQY-UHFFFAOYSA-N 0.000 description 1
- 230000008521 reorganization Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000008247 solid mixture Substances 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 230000019635 sulfation Effects 0.000 description 1
- 238000005670 sulfation reaction Methods 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 235000012222 talc Nutrition 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- 238000001149 thermolysis Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- UDKYUQZDRMRDOR-UHFFFAOYSA-N tungsten Chemical compound [W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W] UDKYUQZDRMRDOR-UHFFFAOYSA-N 0.000 description 1
- 150000003658 tungsten compounds Chemical class 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C6/00—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions
- C07C6/08—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions by conversion at a saturated carbon-to-carbon bond
- C07C6/10—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions by conversion at a saturated carbon-to-carbon bond in hydrocarbons containing no six-membered aromatic rings
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
- B01J31/121—Metal hydrides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0209—Impregnation involving a reaction between the support and a fluid
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
- C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
- C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
- C07C2521/02—Boron or aluminium; Oxides or hydroxides thereof
- C07C2521/04—Alumina
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- C07C2531/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- C07C2531/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
Abstract
The invention relates to a supported metal compound, comprising a support made from aluminium oxide to which a tungsten hydride is grafted. The support may be selected from the homogeneous supports with a composition based on aluminum oxide and from heterogeneous supports made from aluminium oxide with aluminum oxide essentially on the surface of said support. The support may in particular comprise aluminium oxide, mixed aluminium oxides and modified aluminium oxides particularly comprising one or more elements of groups 15 to 17 of the periodic table of the elements, such as phosphorus, sulphur, fluorine or chlorine. A support made from porous, non-porous or mesoporous aluminas is preferred. The degree of oxidation of the tungsten may have a value of from 2 to 6. The tungsten atom is generally bonded to one or several hydrogen atoms and optionally to one or several hydrocarbon groups. According to the invention, the compound may be prepared by a dispersion step and grafting of a tungsten organometallic precursor to the support made from aluminium oxide then hydrogenation of the resulting product. The product may be used as catalyst in reactions of cleavage and recombination of hydrocarbons, particularly in hydrocarbon metathesis reactions most particularly of alkanes. The product has a surprising, extremely high catalytic activity in this type of reaction and in particular, a high selectivity for the formation of n-alkanes with relation to iso-alkanes.
Description
The present invention relates to a kind of metallic compound that is fixed on the solid carrier, the preparation method of this compound and purposes are especially as the purposes of hydrocarbon compound catalysts for metahesis reactions.
Described the replacement(metathesis)reaction method of alkane in International Patent Application WO 98/02244, in this reaction, one or more alkane react on the solid chemical compound that comprises the metal hydride that is grafted to solid carrier.The preparation of this solid chemical compound comprises at first organometallic compound is grafted on the solid carrier, so that form the grafted organometallic compound, by hydrogen or other reductive agent described compound is carried out the hydrogenolysis processing then, thereby generate the metal hydride that is grafted on the carrier.Zhi Bei hydride is used as the catalyzer of alkane replacement(metathesis)reaction like this.Metal in the metal hydride can be selected from the transition metal of the 5th to 6 family in the periodic table of elements, and carrier can be selected from multiple soild oxide.Hydrogenated tantal and the application of this hydride in ethane, propane, butane and isobutane metathesis reaction that is grafted on the silicon-dioxide described among the embodiment of international patent application usually.These embodiment have also described preparation and the application of this hydride in the propane replacement(metathesis)reaction that is grafted on the tungsten hydride on the silicon-dioxide.These are active in grafted hydrogenated tantal or tungsten hydride on the silicon-dioxide in the alkane replacement(metathesis)reaction.Yet searching has more highly active hydrocarbon catalysts for metahesis reactions, still is the important goal in this field.
Be surprised to find very much, in the various possible combination between all the 5th and the 6th group 4 transition metals and soild oxide base carrier, there is not sign to show that the special tungsten of selecting can obtain significantly to improve the metal hydride on the solid carrier of being grafted on to the katalysis of hydrocarbon replacement(metathesis)reaction as transition metal and aluminum oxide as solid carrier.Described improvement comprises significantly improving of catalytic activity, and has increased in the hydrocarbon replacement(metathesis)reaction selectivity of positive hydrocarbon phase for different hydrocarbon.
The present invention at first relates to the metallic compound of the load that comprises alumina-based supports, is grafted with tungsten hydride on the alumina-based supports.Tungsten hydride is grafted on the alumina-based supports, and typically refer to tungsten atom and link to each other with at least one hydrogen atom, and, especially, be connected on the described carrier by at least one singly-bound.
Above and the periodic table of elements of hereinafter mentioning propose in 1991 by IUPAC, wherein each family is numbered as 1 to 18, can be at " CRC Handbook of Chemistry and Physics " the 76th edition (1995-1996), David R.Lide writes, CRC Press, Inc. (USA) finds in publishing.
According to the present invention, this compound mainly contains the tungsten hydride that is grafted on the alumina-based supports.In this compound, carrier can be any carrier based on aluminum oxide, and more especially any wherein aluminum oxide is at the come-at-able especially carrier in the surface of described carrier.This carrier thereby can be selected from based on the composition of aluminum oxide carrier relatively uniformly, especially have in whole carrier (promptly from the center of carrier until the surface) relatively uniformly based on the carrier of the composition of aluminum oxide, can also be selected from the basic inhomogeneous alumina-based supports that comprises aluminum oxide on the surface of carrier.If inhomogeneous carrier, then carrier can comprise deposition, load or be grafted on aluminum oxide on the inoganic solids, described inoganic solids itself can be an inorganic solid support, is selected from metal, oxide compound or sulfide and salt especially, for example is selected from silicon-dioxide and metal oxide.
Carrier can have 0.1 to 1000m
2/ g, especially 0.5 to 800m
2The specific surface area of/g (BET).Specific surface area (BET) is measured according to standard ISO 9277 (1995).
Carrier can comprise especially aluminum oxide, blended aluminum oxide and modification, particularly one or more are by 15 to 17 family element modified aluminum oxides in the periodic table of elements.
Aluminum oxide, be also referred to as common aluminum oxide, typically refer to the aluminum oxide (perhaps containing one or more other oxide compounds that exist with the impurity form that are lower than 2 weight %) that do not contain other oxide compound substantially if. contain one or more other oxide compounds that surpass 2 weight %, this oxide compound can be regarded as the blended aluminum oxide usually so, promptly is combined with the aluminum oxide of at least a other oxide compound.
Carrier can preferably include the aluminum oxide that is selected from porous alumina, non-porous aluminas and mesoporous aluminas.
Porous alumina is commonly referred to " activated alumina " or " transitional alumina ".They are generally corresponding to aluminium oxide Al different, part of hydroxylization
2O
3These are general porous supports that obtain by " activation " processing, and " activation " handled particularly including the oxyhydroxide (for example three aluminium hydroxides) that is selected from aluminium, the oxyhydroxide of aluminum oxide and the precursor of gel aluminium hydroxide are heat-treated (or dehydration).Activation treatment can be eliminated water and the part of hydroxyl that is present in the precursor, stays some residual hydroxyls and specific pore structure.The surface of porous alumina generally comprises the complex mixture of aluminium and Sauerstoffatom and according to specific crystal form bonded, produce the hydroxyl ion of acid sites and alkalescence point especially.Solid carrier can be selected from porous alumina gama-alumina (gamma-aluminum oxide), η-aluminum oxide (eta-aluminum oxide), δ-aluminum oxide (delta-aluminum oxide), θ-aluminum oxide (theta-aluminum oxide), κ-aluminum oxide (kappa-aluminum oxide), ρ-aluminum oxide (rho-aluminum oxide) and χ-aluminum oxide (chi-aluminum oxide), and is preferably selected from gama-alumina and η-aluminum oxide.These different crystal forms depend primarily on selection and the activation treatment condition, particularly temperature and pressure of precursor.Activation treatment can be for example carried out under airflow or another gas (particularly rare gas element) flow down, may be selected to be 100 to 1000 ℃, preferred 200 to 1000 ℃ temperature.
Can also use porous or half porous aluminum oxide, they make by aforementioned activation treatment, special processing under 600 to 1000 ℃ temperature.This porous or half porous aluminum oxide can comprise the mixture of porous alumina and non-porous aluminas, ratio is in particular 20 to 80 weight %, described porous alumina is at least a aforementioned crystal form, as gama-alumina, η-aluminum oxide, δ-aluminum oxide, θ-aluminum oxide, κ-aluminum oxide, ρ-aluminum oxide or χ-aluminum oxide, described non-porous aluminas is Alpha-alumina particularly.
Porous alumina generally is the thermal decomposition product of three aluminium hydroxides, hydroxide aluminum oxide (or hydrated aluminum oxide) and gel aluminium hydroxide (alumina gel).
General formula is Al (OH)
3=Al
2O
33H
2Three aluminium hydroxides of O can be different crystal form exist, as gibbsite or gibbsite (α-Al (OH)
3), bayerite (β-Al (OH)
3) or the promise gibbsite.Three aluminium hydroxides can precipitate in the solution that is generally alkalescence by aluminium salt and obtain.
General formula is AlO (OH)=Al
2O
3H
2The hydroxide aluminum oxide of O also can be different crystal form exist, as diaspore (β-AlO (OH)) or boehmite (or α-AlO (OH)).Diaspore can obtain from the clay of some type or bauxite, and can synthesize by in about 150 ℃ gibbsite being heat-treated, and perhaps synthesizes by under 380 ℃ of pressure at 50MPa boehmite being carried out hydrothermal treatment consists.Boehmite can easily make by heating gelatinous precipitate (with ammonia aluminum salt solution being carried out deepfreeze obtains).The hydroxide aluminum oxide also can be by aluminium the hydrolysis of alcoholate obtain.
Gel aluminium hydroxide (or alumina gel) generally is many oxyhydroxide of aluminium, particularly has following general formula:
nAl(OH)
3·(n-1)H
2O (1)
N is 1 to 8 number in the formula.Gel aluminium hydroxide can obtain by being selected from a kind of of following method: the thermolysis of aluminium salt (as aluminum chloride); The electrolysis of aluminium salt (as the mixture of Tai-Ace S 150 and alkali metal sulfates); The hydrolysis of the alcoholate of aluminium (as aluminum methylate); The precipitation of aluminate (as basic metal or alkali earth metal aluminate); The precipitation of aluminium salt for example, makes Al
2(SO
4)
3The aqueous solution and ammonia or NaAlO
2The aqueous solution with acid, NaAlO
2The aqueous solution and Al
2(SO
4)
3Contact then can be aging and dry to remove moisture with the precipitation that obtains. and gel aluminium hydroxide generally is the form of amorphous alumina gel, particularly the pseudobochmite form.
Porous alumina can have 100 to 1000m
2/ g, preferred 300 to 1000m
2/ g, particularly 300 to 800m
2/ g, particularly 300 to 600m
2The BET specific surface area of/g.They can further have the 1cm of being less than or equal to
3/ g, preferably be less than or equal to 0.9cm
3/ g, particularly be less than or equal to 0.6cm
3The ratio pore volume of/g.
Carrier can also comprise non-porous aluminas, preferred Alpha-alumina (alpha-aluminum oxide), and it is commonly referred to " incinerating aluminum oxide " or " aluminum oxide that overdoes ".Alpha-alumina exists with native state, is called " corundum ".It can followingly synthesize usually: be higher than 1000 ℃, preferably be higher than under 1100 ℃ the temperature, thermal treatment or calcining are selected from the precursor of aluminium salt, hydroxide aluminum oxide, three aluminium hydroxides and aluminum oxide (as gama-alumina) especially.It can comprise impurity with the ratio that is lower than 2 weight %, preferably is lower than 1 weight %, and other oxide compound for example is as Fe
2O
3, SiO
2, TiO
2, CaO, Na
2O, K
2O, MgO, SrO, BaO and Li
2O.Non-porous aluminas (as Alpha-alumina) can have 0.1 to being lower than 300m
2/ g, preferred 0.5 to 300m
2/ g, particularly 0.5 to 250m
2The specific surface area of/g (BET).
Carrier can also comprise mesoporous aluminas, and it has 100 to 800m especially
2The specific surface area of/g (BET).It is the hole of 2nm to 0.05 μ m that mesoporous aluminas generally has width.
Carrier can also comprise the blended aluminum oxide.The blended aluminum oxide generally is meant with preferred 2% to being lower than 80%, particularly 2% to being lower than 50%, particularly 2% to being lower than 40% or even 2% to being lower than 30% the weight ratio and the aluminum oxide of at least a other oxide-bonded.Other oxide compound can be the oxide compound of element M, and M is selected from the metal of 1 to 13 family in the periodic table of elements and the element of 14 families, except the carbon.More specifically, they can be the oxide compounds that is selected from the element M of basic metal, alkaline-earth metal, transition metal and the periodic table of elements 13 and 14 family's elements (except the carbon).Transition metal generally comprises periodictable 3 to 11 family's metals, particularly 21 to 29,39 to 47,57 to No. 79 elements (comprising group of the lanthanides) and actinide elements.Other oxide compound of element M is preferably selected from the 3rd to 7 group 4 transition metal in the periodictable, group of the lanthanides, actinium series and 13 and 14 family's elements (except the carbon).More specifically, they can be selected from the oxide compound of silicon, boron, gallium, germanium, titanium, zirconium, cerium, alum, niobium, tantalum, chromium, molybdenum and tungsten.
The blended aluminum oxide can be selected from anhydrous aluminates, spinel and silico-aluminate.Especially, anhydrous aluminates can be selected from anhydrous alkali metal aluminate, as anhydrous lithium aluminate (LiAlO
2) or anhydrous sodium aluminate (NaO
2Al
2O
3) and anhydrous alkali earth metal aluminate, as anhydrous calcium aluminate (3CaOAl
2O
3) or anhydrous beryllium aluminate (BeOAl
2O
3).Spinel can be selected from the oxide compound of the aluminium that is combined with bivalent metal oxide especially, and is selected from magnesia spinel (MgAl especially
2O
4), calcium spinel (CaAl
2O
4), zinc spinel (ZnAl
2O
4), galaxite (MnAl
2O
4), hercynite (FeAl
2O
4) and cobalt spinel (CoAl
2O
4).Aluminosilicate can be selected from clay, talcum, mica, feldspar, micropore silico-aluminate (particularly molecular sieve and zeolite) especially.
Carrier also can comprise the aluminum oxide of modification, particularly passes through the aluminum oxide of element (as phosphorus, sulphur, the fluorine or chlorine) modification of one or more periodic table of elements 15 to 17 families, preferred 16 to 17 families.Carrier can comprise aluminum oxide peracid or sulfation, sulfuration, chlorination or fluorizated aluminum oxide especially.
Carrier can be to form the evenly carrier of (particularly on whole carrier). carrier also can be the inhomogeneous carrier of alumina base, in this carrier, foregoing aluminum oxide, the aluminum oxide of blended aluminum oxide or modification mainly is arranged on the carrier surface, and the center of carrier is mainly by being selected from metal especially, oxide compound, the inoganic solids of sulfide and salt (as silicon-dioxide or metal oxide) constitutes. and inhomogeneous carrier can pass through a kind of dispersion with the precursor of alumina base compound mentioned above, precipitating or be grafted on the described inoganic solids and prepare. described precursor can be selected from aluminium hydroxide especially, can be selected from three aluminium hydroxides especially, hydroxide aluminum oxide and gel aluminium hydroxide. gel aluminium hydroxide is preferred, as previously mentioned, it is called as alumina gel or unformed aluminum oxide. and inhomogeneous carrier can be prepared as follows especially: by sol-gel method, or by the organometallics of being convenient to especially be grafted on the inoganic solids described precursor is handled.
Compound of the present invention is generally particle form, and different shape and size can be arranged, and particularly has the mean particle size of 10nm to 5mm, preferred 20nm to 4mm.The particle of carrier can be their natural shape, maybe can be through being shaped having specific shape, and particularly spherical, spherical, semisphere, hemispherical, cylindric or cube shaped, or be ring-like, sheet shape, dish type or ball type.
Compound of the present invention mainly comprises the tungsten hydride that is grafted on the alumina-based supports.The oxidation state of the tungsten in the metallic compound of this load can be 2 to 6 value, is preferably 4 to 6.Tungsten atom is connected on the solid carrier especially, connects by at least one singly-bound especially.It can pass through singly-bound (W-H) and is connected with one or more hydrogen atoms, and can randomly connect one or more alkyl R, particularly connects by carbon-tungsten singly-bound or multiple bond.The singly-bound number that the number that is connected a hydrogen atom on the tungsten atom depends on the oxidation state of tungsten, link to each other tungsten atom and carrier, and randomly depend on the singly-bound that described tungsten atom is connected with alkyl R or the number of multikey.Like this, the number that is connected to a hydrogen atom on the tungsten atom can equal 1 at least, and maximum equals 5, and can be preferably 1 to 4, preferably between 1 to 3.Tungsten hydride is grafted to and is meant generally on the alumina base solid carrier that tungsten atom passes through at least one singly-bound and links to each other with carrier, links to each other with at least one Sauerstoffatom in the aluminum oxide by at least one singly-bound (W-OAl) more especially.Tungsten atom is connected with carrier, particularly passes through the singly linked singly-bound number of W-OAl, depend on the oxidation state of tungsten and the number of other key that is connected tungsten atom, be generally equal to 1,2 or 3.
Tungsten atom in the The compounds of this invention can randomly pass through one or more carbon-tungsten singly-bound, two key or triple bond and be connected with one or more alkyl R.Alkyl R can be identical or different, saturated or unsaturated alkyl, 1 to 20 carbon atom is particularly arranged, preferably have the alkyl of 1 to 10 carbon atom, and can randomly comprise the silicon in the silicon, particularly organosilicon alkyl.They can be selected from alkyl, particularly straight or branched, aliphatic or alicyclic alkyl, for example alkyl, alkylidene group or alkylidene (alkylidyne), particularly C especially
1To C
10; Can be selected from aryl, particularly C
6To C
12Aryl; And can be selected from aralkyl, arylmethylene alkyl and fragrant alkylidene (aralkylidyne), particularly C
7To C
14.
Tungsten atom in the grafted tungsten hydride can pass through one or more carbon-tungsten singly-bound, two key or triple bond and link to each other with alkyl R.This key can be carbon-tungsten singly-bound, especially σ key: in the case, alkyl R can be alkyl, especially straight chain or branched-chain alkyl; Or aryl, for example phenyl; Perhaps arylmethylene alkyl (aralkylene) is (C as phenmethyl or general formula
6H
5-CH
2-CH
2-) group.Alkyl typically refer to from alkane, alkene or alkynes or even the organosilicon molecule carbon atom remove hydrogen atom and the unit price aliphatic residue that obtains, methyl (CH for example
3-), ethyl (C
2H
5-), propyl group (C
2H
5-CH
2-), neo-pentyl [(CH
3)
3C-CH
2-], allyl group (CH
2=CH-CH
2-), alkynyl (R-C ≡ C-), especially ethynyl (CH ≡ C-), perhaps new silyl [neosilyl, (CH
3)
3Si-CH
2-].Alkyl for example can use molecular formula (R '-CH
2-) expression, wherein R ' can be the straight or branched alkyl.
Described key can also comprise carbon-tungsten two key, especially π keys: in the case, alkyl R can be alkylidene group, particularly straight chain and side chain; It maybe can be arylmethylene alkyl.Alkylidene group generally be meant from alkane, alkene or alkynes or even the organosilicon molecule identical carbon atoms remove two hydrogen atoms and the divalent aliphatic residue that obtains, for example, methylene radical (CH
2=), ethylidene (CH
3-CH=), propylidene (C
2H
5-CH=), inferior neo-pentyl [(CH
3)
3C-CH=] or acrol (CH
2=CH-CH=).The also available for example general formula of alkylidene group (R '-CH=) expression, R ' represents the straight or branched alkyl in the formula.Arylmethylene alkyl generally is meant the divalent aliphatic residue that obtains from removing two hydrogen atoms by the identical carbon atoms aryl ramose alkyl, thiazolinyl or the alkynyl.
Described key can also comprise carbon-tungsten triple bond: in this case, alkyl R can be alkylidene, particularly straight or branched, or fragrant alkylidene.Alkylidene generally be meant from alkane, alkene or alkynes or even the organosilicon molecule identical carbon atoms remove three hydrogen atoms and the trivalent aliphatic residue that obtains, for example, ethylidine (CH
3-C ≡), propylidyne (C
2H
5-C ≡), inferior neo-pentyl [(CH
3)
3C-C ≡], inferior allyl group (CH
2=CH-C ≡).Alkylidene can be used general formula (R '-C ≡) expression, and wherein R ' represents the straight or branched alkyl.The virtue alkylidene generally is meant the trivalent aliphatic residue that obtains from removing three hydrogen atoms by the identical carbon atoms aryl ramose alkyl, thiazolinyl or the alkynyl.
More specifically, alkyl R can be selected from methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, neo-pentyl, allyl group, inferior neo-pentyl, acrol, inferior neo-pentyl and new silyl.
The tungsten atom of The compounds of this invention can be cooperated by one or more hydrocarbon part, particularly aromatics or carbonyl ligands.
Can be schematically represent to be grafted on tungsten hydride on the alumina-based supports with following formula:
Wherein W, Al, O and H represent tungsten, aluminium, oxygen and hydrogen atom respectively, one or more atoms of elements of foregoing other oxide compound of M representative, R represents foregoing alkyl, x, y, w and z are integers, (w+x+y+z) and be 2 to 6, and x=1 to 3, y=1 to 5, w=0 to 4, z=0 to 2.In formula (2), key--(Al-O) with--(M-O) is represented respectively aluminium atom and atom M and the composed atom of alumina-based supports, the singly-bound or the multiple bond that particularly are connected with a Sauerstoffatom in this carrier.
The distinctive one or more absorption bands of (W-H) key appear in The compounds of this invention usually in infrared spectra, the frequency of these bands can change with the coordination situation of tungsten, and can be depending on especially tungsten and carrier, and alkyl R, and other hydrogen atom between chemical bond number.For example, at least 1903 and 1804cm
-1The place finds two absorption bands, and these absorption bands particularly described (W-H) key is distinctive, and particularly under following situation: (W-OAl) key will be connected with Sauerstoffatom with identical tungsten atom, and Sauerstoffatom self is connected with aluminium atom in the Alpha-alumina.As a comparison, the tungsten hydride that is grafted on silica supports soil under the similarity condition generally occurs being positioned at 1940 and 1960cm in infrared spectra
-1Two absorption bands at least one, this is different with the front, and particularly described (W-H) key is distinctive, and particularly under following situation: (W-OSi) key will be connected with Sauerstoffatom with identical tungsten atom, and Sauerstoffatom self is connected with Siliciumatom in the silicon-dioxide.
Can characterize in the The compounds of this invention another method that has (W-H) key is with proton magnetic resonance (PMR) (solid
1H-NMR) under 500MHz, measure, wherein chemical displacement value (the δ of tungsten hydride
W-H) equal 10.6ppm (1,000,000/).
Compound of the present invention can further comprise aluminum hydride, particularly on the surface of carrier, particularly near the grafted tungsten hydride.Aluminum hydride can be by opening alumina (aluminoxane) bridge (general formula is Al-O-Al) that is present in especially on the carrier surface and forming by the reaction between hydrogen atom in the grafted tungsten hydride and the alumina bridge opened like this.Characterize the deutration that simple experiment that aluminum hydride is present in the tungsten hydride next door in the The compounds of this invention comprises described compound.This experiment can followingly be carried out: 66.7kPa (kPa) absolute pressure under, 25 to 80 ℃, preferably equal to make compound of the present invention contact 15 minutes under 60 ℃ the temperature with deuterium atmosphere.Thus, carry out optionally deutration under these conditions, this reaction can make the hydrogen atom in (W-H) key be replaced by D atom, forming new (W-D) key, its in infrared spectra in 1293 and 1393cm
-1Have two absorption bands.And (Al-H) hydrogen atom in the key does not change, and these keys can pass through 1914cm in infrared spectra
-1The absorption band at place characterizes.
The invention still further relates to the method for the metallic compound of preparation load.Compound of the present invention is mainly the form that is grafted on the tungsten hydride on the alumina-based supports, can be prepared by a method comprising the following steps:
(1) organo-metallic tungsten precursor (Pr) disperses and is grafted on step on the alumina-based supports, and tungsten is connected or complexing with at least a hydrocarbon part especially in this precursor, thereby forms hydrocarbon compound or the complex compound that is grafted on the tungsten on the described carrier, then
(2) hydrocarbon compound of the grafted tungsten that is obtained by the preceding step or the hydrogenolysis step of complex compound are grafted on tungsten hydride on the described carrier with formation.
Organo-metallic tungsten precursor Pr preferably comprises and is connected with one or more hydrocarbon parts or the tungsten atom of complexing.Tungsten atom can pass through (carbon-tungsten) singly-bound, two key or triple bond especially and be connected with carbon in the hydrocarbon part.The hydrocarbon part can be identical or different, saturated or unsaturated alkyl, particularly aliphatic series or alicyclic alkyl, preferably C
1To C
20, C especially
1To C
10, and can be selected from aforementioned alkyl R especially.The number of the alkyl that is connected with tungsten atom depends on the oxidation state of tungsten among the precursor Pr, especially can be, and can preferably have any value between 2 to 6 greater than 0 and the maximum highest oxidation state that equals tungsten, and particularly 4 to 6.
Precursor Pr can comprise the tungsten atom special and complexing of one or more hydrocarbon part, and the oxidation state of tungsten is zero in this case.The hydrocarbon part can be selected from aromatic ligand or carbonyl ligands.Thereby precursor Pr can be selected from two aromatic hydrocarbons tungsten and tungsten hexacarbonyl.
Before dispersion and grafting step, can calcine and/or dehydroxylation alumina-based supports in advance.The calcining of carrier can be will randomly be present in the oxidation of coal in the carrier and with the form of carbonic acid gas the mode of its elimination to be carried out.It can followingly carry out: especially in dry air stream, under the temperature that is lower than the carrier sintering temperature, for example under 100 to 1000 ℃, preferred 200 to 800 ℃ temperature, be lower than, be equal to or higher than under the atmospheric pressure, carrier is carried out the oxidation heat treated, be enough to eliminate the time (can be 0.1 to 48 hour) of carbonic acid gas.
Carrier can also carry out another pre-treatment, i.e. dehydroxylation.This step can be can be randomly eliminating residual water and the mode of a part of hydroxyl is carried out from carrier, leave the hydroxyl of residual quantity on the surface of carrier especially, and randomly form alumina bridge (general formula is Al-O-Al).Dehydroxylation can followingly carry out: in inert gas flow, for example in nitrogen gas stream, argon gas stream or helium flow, under preferred pressure below atmospheric pressure, for example 10
-4Pa to 10
2KPa, preferred 10
-2Under the absolute pressure of Pa to 50kPa, under the temperature that is lower than the carrier sintering temperature, for example under 100 to 1000 ℃, preferred 200 to 800 ℃ temperature, carrier is heat-treated, be enough in carrier, to stay the time (this can be 0.1 to 48 hour) of the hydroxyl and/or the alumina bridge of suitable residual quantity.The dehydroxylation step should realize behind calcining step.
Dispersion and grafting step can be by distillations, by carrying out by the dipping of solvent or by dry blending.Under the situation that adopts sublimation step, under pressure below atmospheric pressure,, precursor Pr (it is solid-state under normal operation usually) is heated especially guaranteeing the carrier distillation and moving to gaseous state under the temperature condition of carrier surface.Distillation can be under-30 to 200 ℃ temperature, especially 10
-4Under the absolute pressure of 1Pa, carry out.Can monitor the grafting of precursor Pr on carrier by infrared spectra.Any excess precursor Pr that is not grafted on the carrier can eliminate by anti-sublimation.
Dispersion and grafting step also can be undertaken by the dipping by solvent.In this case, precursor Pr can be dissolved in polarity or the nonpolar organic solvent (as pentane or ether).Dipping can be undertaken by alumina-based supports is contacted with the solution of previously prepared precursor Pr.Dipping can be under-80 to 200 ℃ the temperature, in inert atmosphere (for example nitrogen, argon gas or helium atmosphere) and preferably under agitation carry out.The hydrocarbon compound of the tungsten on the carrier or the suspension of complex compound have so just been obtained to be grafted to.Any excess precursor that is not grafted on the carrier can be by removing with organic solvent washing, used organic solvent can with steeping process in used identical or different.
Dispersion and grafting step can also be passed through dry blending under the situation that does not have liquid or liquid solvent, particularly the mechanical dry mixing is carried out. in this case, under the situation that does not have liquid or liquid solvent, pass through mechanical stirring especially, and at inert atmosphere (nitrogen for example, argon gas or helium atmosphere) in, the precursor Pr that is solid form is mixed with alumina-based supports, thereby form two kinds of solid mixtures. during dry blending or afterwards, can carry out heat treated and/or the processing under pressure below atmospheric pressure, so that precursor Pr moves and reacts with carrier. any precursor that is not grafted on the carrier can be removed by anti-sublimation or with organic solvent washing.
The preparation of The compounds of this invention can comprise second step that is called hydrogenolysis.This is included in the hydrocarbon compound that is grafted on the tungsten on the carrier for preparing in the preceding step or the hydrogenolysis of complex compound.Usually carry out this reaction and be grafted to tungsten hydride on the carrier with formation.Hydrogenolysis typically refers to the division of molecule, and hydrogen is connected to two splitted parts.Particularly, dissociative reaction occur in especially be grafted on the tungsten atom on the carrier and be fixed on the described tungsten atom or and the carbon atom of the precursor Pr of described tungsten atom complexing between.Hydrogenolysis can be undertaken by the hydrogen or the reductive agent that the hydrocarbon compound or the complex compound of grafted tungsten can be transformed into the grafted tungsten hydride especially.Hydrogenolysis can be by making grafted tungsten hydrocarbon compound or complex compound contact with reductive agent with hydrogen and carry out.It can followingly carry out: in nitrogen atmosphere maybe when using reductive agent in inert gas atmosphere, 10
-2Under the absolute pressure of 10MPa, under 20 to 500 ℃ temperature, carried out 0.1 to 48 hour.
The invention still further relates to the purposes of The compounds of this invention in the method for utilizing hydrocarbon division and recombining reaction.Be particularly related to the purposes of The compounds of this invention in following method:, make hydrocarbon with the carbon backbone chain that is modified by making at least a aliphatic hydrocrbon and himself or reacting with at least a other aliphatic hydrocrbon or with at least a aromatic hydrocarbon or the cyclic hydrocarbon that is replaced by at least a alkyl.In this method, can use aliphatic hydrocrbon, aliphatic hydrocrbon is selected from linear aliphatic hydrocarbon, particularly C
2To C
30, preferred C
2To C
20The linear aliphatic hydrocarbon, branched aliphatic hydrocarbons, particularly C
4To C
30, preferred C
4To C
20Branched aliphatic hydrocarbons; The perhaps aromatic hydrocarbon that is replaced by at least a alkyl, this aromatic hydrocarbon is selected from by at least a straight or branched alkyl, particularly C
1To C
24, preferred C
1To C
14The C that replaces of straight or branched alkyl
7To C
30, preferred C
7To C
20Aromatic hydrocarbon; The perhaps cyclic hydrocarbon that is replaced by at least a alkyl, this cyclic hydrocarbon is selected from by at least a straight or branched alkyl, particularly C
1To C
27, preferred C
1To C
17The C that replaces of straight or branched alkyl
4To C
30, preferred C
4To C
20Cyclic hydrocarbon.This method is described in the International Patent Application WO 98/02244 especially.This method can be under 20 to 600 ℃, preferred 50 to 500 ℃ temperature, carry out 0.1 to 100MPa, under preferred 0.1 to 50MPa the absolute pressure.It can be preferably hydrogen or " scene " generate hydrogen reagent in the presence of carry out, for example depress and carry out at 0.01 to 50MPa, preferred 0.1 to 20MPa hydrogen branch.The compounds of this invention is particularly useful as catalyzer, is particularly useful as the catalyzer of the replacement(metathesis)reaction of hydrocarbon.It can be in the manufacturing processed of hydrocarbon or the manufacturing processed that is independent of hydrocarbon activate or regenerate by contacting with reagent that hydrogen or " scene " generate hydrogen.
Compound of the present invention can be particularly useful as the catalyzer of the replacement(metathesis)reaction of hydrocarbon (particularly alkane).Particularly outstanding is, it shows high catalytic activity and with respect to the selectivity of the very high positive hydrocarbon of generation (promptly having straight chain hydrocarbon) that generates branched-chain hydrocarbon, particularly different hydrocarbon in the replacement(metathesis)reaction of hydrocarbon and/or homologation (or disproportionation) reaction.Compound of the present invention shows very high catalytic activity especially in the replacement(metathesis)reaction of alkane and/or homologation (or disproportionation) reaction, and shows the selectivity with respect to the very high generation normal alkane that generates isoalkane simultaneously.
Compound of the present invention also can be particularly useful as by preparing the catalyzer of the method for hydrocarbon by methane and at least a other aliphatic hydrocrbon or with the reaction of at least a aromatic hydrocarbon that is replaced by at least a alkyl or cyclic hydrocarbon.This method has description in International Patent Application WO 01/04077.Described method is included under the existence of metallic compound of load of the present invention methane is contacted with at least a above-mentioned hydrocarbon.The reaction that is caused by this contact normally comprises the hydrocarbon replacement(metathesis)reaction of hydrocarbon division and reorganization, also is simultaneously to incorporate methane in these hydrocarbon reaction.These reactions are commonly referred to as " methane decomposition (methanolysis) " reaction.In the method, methane can use with at least a other aliphatic hydrocrbon, and described hydrocarbon is selected from: linear aliphatic hydrocarbon, particularly C
2To C
30, preferred C
3To C
20The linear aliphatic hydrocarbon; Branched aliphatic hydrocarbons, particularly C
4To C
30, preferred C
4To C
20Branched aliphatic hydrocarbons; The perhaps aromatic hydrocarbon that is replaced by at least a alkyl, this aromatic hydrocarbon is selected from by at least a straight or branched alkyl, particularly C
1To C
24, preferred C
1To C
14The C that replaces of straight or branched alkyl
7To C
30, preferred C
7To C
20Aromatic hydrocarbon; The perhaps cyclic hydrocarbon that is replaced by at least a alkyl, this cyclic hydrocarbon is selected from by at least a straight or branched alkyl, particularly C
1To C
27, preferred C
1To C
17The C that replaces of straight or branched alkyl
4To C
30, preferred C
4To C
20Cyclic hydrocarbon.In the method, also can use the mixture of methane and one or more other aliphatic hydrocrbons and/or cyclic hydrocarbon, as Sweet natural gas, oil liquefied gas or LGP, moisture or wet natural gas (namely for methane and C
2To C
5Or C
3And/or C
4The mixture of alkane), natural gas liquids or NGL or C
1To C
6, or C
1To C
5, or C
1To C
4, or C
1To C
3, or C
1To C
2Light fractions.This reaction can be under 20 to 600 ℃, preferred 50 to 500 ℃ temperature, depress at 0.1 to 100MPa, preferred 0.1 to 50MPa methane branch especially, and can be randomly hydrogen or " scene " generate hydrogen reagent in the presence of, for example 0.01 to 50MPa, preferred 0.1 to 20MPa hydrogen branch depresses and carries out.
Compound of the present invention can also be used as catalyzer in the method by methane and himself prepared in reaction alkane, especially ethane.More particularly, this is to comprise the method that methane is contacted with compound of the present invention.This method is known as the conversion of methane to ethane usually.In this case, the particularly non-oxide method for transformation of the method for methane conversion, the catalyzed conversion by methane carries out especially, can make methane be converted into ethane basically, has high ethane selectivity especially.This method can be under 20 to 800 ℃, preferred 50 to 600 ℃ temperature, carry out 0.01 to 100MPa, under preferred 0.1 to 50MPa the absolute pressure.
Compound of the present invention can also be used for preparing by the intersection replacement(metathesis)reaction between at least a raw material hydrocarbon and the described compound method of hydrocarbon.This method is described in the International Patent Application WO 00/27781 especially.Intersect the particularly reaction of following acquisition of replacement(metathesis)reaction: will link to each other with tungsten hydride of the present invention or the alkyl or the part division of complexing, perhaps with described alkyl or part with at least a other alkyl of generation is recombinated by described raw material hydrocarbon division.In the method, operable raw material hydrocarbon is selected from: aliphatic straight chain or branched-chain hydrocarbon, especially C
2To C
30, preferred C
2To C
20; At least by the cyclic hydrocarbon, particularly C of an alkyl replacement
4To C
30, preferred C
4To C
20Cyclic hydrocarbon, described alkyl is a straight or branched, particularly C
1To C
27, preferred C
1To C
17Alkyl.Compound of the present invention comprises at least one the alkyl R that links to each other with tungsten hydride or hydrocarbon part especially.This method can be under 20 to 500 ℃, preferred 50 to 400 ℃ temperature, carry out 0.01 to 50MPa, under preferred 0.1 to 20MPa the absolute pressure.
Compound of the present invention can also be especially be used as catalyzer in the prepared in reaction by raw material hydrocarbon polymkeric substance and hydrogen has the method for the hydrocarbon of carbon backbone chain of modification or hydrocarbon oligomer or polymkeric substance.This method is described among the international patent application EP 0840771 especially.The raw material hydrocarbon polymkeric substance can be one or more alkene monomers or vinyl monomer (being total to) polymkeric substance, particularly polyolefine, for example polyethylene, polypropylene, poly-1-butylene, polyisobutene, ethene and at least a C
3To C
8The multipolymer of α-alkene, propylene and at least a C
4To C
8The multipolymer of the multipolymer of α-alkene, iso-butylene and 1-butylene or aromatics polyvinyl such as polystyrene or poly-(alpha-methyl styrene).The weight-average molecular weight Mw of hydrocarbon polymer can be 10
3To 10
7, preferred 10
4To 10
6This method can followingly be carried out: have hydrogen and randomly existing especially under the condition of solvent medium that can the dissolving raw material polymkeric substance, perhaps stock polymer is under the temperature condition of molten state in contact process, stock polymer is contacted with loaded metal compound of the present invention.This method can be depressed under 20 to 400 ℃, preferred 50 to 300 ℃ temperature, at 0.001 to 20MPa, 0.01 to 10MPa hydrogen branch and carry out 5 minutes to 100 hours, preferred 10 minutes to 50 hours.This method can be especially in increasing the field of centrifugal force, for example 5 to 1000 times in gravitational, in the disc type reactor of rotation, carry out especially.In this case, can be 1 second to 5 minutes duration of contact, preferred 2 seconds to 2 minutes.
It is particularly advantageous using compound of the present invention in one of aforesaid method, because especially in the replacement(metathesis)reaction of hydrocarbon (particularly alkane), this compound is at carbon-to-carbon, carbon-hydrogen and randomly the division of tungsten-carbon bond and the catalytic activity in the recombining reaction enlarge markedly.In addition, in the replacement(metathesis)reaction of alkane, compound of the present invention shows the selectivity with respect to the high generation nalka of the different hydrocarbon that generates.
Following embodiment is used to illustrate the present invention.
Embodiment 1: preparation is grafted on the tungsten hydride on the aluminum oxide
In preliminary step, the mean particle size that 530mg Johnson Mattey (Britain) is sold is that 40 μ m, specific surface area (BET) are 200m
2/ g, contain 90 weight % aluminum oxide and 9 weight % water Alpha-alumina in dry air stream in 500 ℃ of calcination processing 15 hours, then 10
-2Under the absolute pressure of Pa in 500 ℃ of processed 15 hours, thereby make calcining in this way and hydroxylated aluminum oxide in infrared spectra respectively at 3774,3727 and 3683cm
-1Three absorption bands appear, the feature of their (AlO-H) keys that is residual.
In the first step, in glass reactor, in argon atmospher and under 25 ℃, add the aluminum oxide that 530mg prepares previously, add then and contain the solution of 6ml Skellysolve A that 300mg is used as precursor Pr and has the inferior neo-pentyl tungsten of three (neo-pentyls) of following general formula:
W[-CH
2-C(CH
3)
3]
3[≡C-C(CH
3)
3] (3)
Institute's mixture that obtains kept 3 hours down at 25 ℃.When finishing at this moment, obtained to be grafted on the organo-metallic tungsten compound on the aluminum oxide, unreacted excessive precursor Pr is by removing 25 ℃ of washings with Skellysolve A.Drying grafted metal organic tungsten compound in this way in a vacuum.It contains the tungsten of 1.5 weight %, and has following general formula:
(Al-O)
xW[-CH
2-C(CH
3)
3]
y[＝CH-C(CH
3)
3] (4)
Wherein x=1 and y=2
In second step, isolate the grafted organo-metallic tungsten compound that 40mg obtains previously, in glass reactor, carry out the hydrogenolysis processing by contacting with hydrogen, under the absolute hydrogen pressure of 73kPa, carried out 15 hours in 150 ℃.When this finishes time, with reactor cooling to 25 ℃, obtained compound of the present invention (W/Al-1), and in argon gas, separated, it contains the tungsten hydride that is grafted on the aluminum oxide especially.This compound (W/Al-1) contains the tungsten of 1.5 weight %, and respectively at infrared spectra 1903 and 1804cm
-1The place has two absorption bands, and this is grafted to the feature of (W-H) key on the aluminum oxide especially.
Embodiment 2: preparation is grafted on the tungsten hydride on the aluminum oxide
Identical among the precalcining of Alpha-alumina and dehydrating step and the embodiment 1.
In the first step, isolate the aluminum oxide that 53mg prepares above, and it is introduced in the glass reactor under 25 ℃ of argon atmosphers.Then, the precursor Pr of the general formula (3) that embodiment 1 is used introduces this reactor.Reactor is heated to 70 ℃ then and reaches 2 hours, thereby precursor is sublimate on the aluminum oxide, and form the organo-metallic tungsten compound that is grafted on the aluminum oxide.When this time finishes, by eliminating responseless excess precursor Pr at 70 ℃ of following anti-sublimations.Then, with reactor cooling to 25 ℃, isolate grafted organo-metallic tungsten compound in this way under argon atmospher, it contains the tungsten of 3.7 weight % and has above-mentioned general formula (4).
Second step was fully to carry out according to the step identical with embodiment 1, the different organo-metallic tungsten compounds on the aluminum oxide of being grafted to that prepare previously that are to use.Obtain (W/Al-2) of the present invention compound like this, it comprises the tungsten hydride that is grafted on the aluminum oxide, and contains the tungsten of 3.7 weight %.It is at infrared spectra 1903 and 1804cm
-1The place has two absorption bands respectively, and this is the feature that is grafted to (W-H) key on the aluminum oxide especially.
Compound (W/Al-2) is carried out selectivity deuterate experiment, prove that it contains tungsten hydride and aluminum hydride, the two all is grafted on the aluminum oxide.The sample of compound (W/Al-2) is placed in the glass reactor, make it in this reactor, under the absolute pressure of 66.7kPa, 60 ℃ temperature, contact 15 minutes then with deuterium atmosphere.This is when finishing time, with reactor cooling to 25 ℃, and isolates such deuterated solid chemical compound in argon atmospher, described compound on infrared spectra in 1914cm
-1An absorption band occurs, this is the feature of (Al-H) key of changing of the deutration that do not carried out under these conditions.Observe in addition and characterize 1903 and the 1804cm that is grafted on (W-H) key on the aluminum oxide
-1The absorption band at place disappears, and replaces 1293 and 1393cm respectively
-1The absorption band at place characterizes (W-D) key be grafted on the aluminum oxide and formed by the deuterate of (W-H) key.
Embodiment 3: preparation is grafted on the tungsten hydride on the aluminum oxide
Identical among the precalcining of Alpha-alumina and dehydrating step and the embodiment 1.
In the first step, isolate the previously prepared aluminum oxide of 2g, and under argon atmospher, be introduced into 25 ℃ and be equipped with in the glass reactor that stirs magneton.Then, the precursor Pr that in this reactor, adds the used general formula (3) of 305mg embodiment 1.This reactor is heated to 66 ℃, and stirs the drying mixture that is equipped with 4 hours of obtaining.This is when finishing time, with reactor cooling to 25 ℃, then with Skellysolve A at 25 ℃ of these mixtures of washing.The solid chemical compound of washing like this is dry in a vacuum, in argon atmospher, separate then, to obtain being grafted on the organo-metallic tungsten compound on the aluminum oxide, it contains the tungsten of 3.9 weight %, and has above-mentioned general formula (4).
Second step was fully to carry out according to the step identical with embodiment 1, the different organo-metallic tungsten compounds on the aluminum oxide of being grafted to that prepare previously that are to use.Like this, obtain (W/Al-3) of the present invention compound, it comprises the tungsten hydride that is grafted on the aluminum oxide, and contains the tungsten of 3.9 weight %.It is at infrared spectra 1903 and 1804cm
-1The place has two absorption bands respectively, and this is grafted onto the feature of (W-H) key on the aluminum oxide.In addition, when nucleus magnetic resonance (solid by 500MHz
1When H-NMR) detecting, it has the tungsten hydride chemical displacement value (δ that equals 10.6ppm (1,000,000/)
W-H).
Embodiment 4 (Comparative Examples): preparation is grafted on the tungsten hydride on the silicon-dioxide
In preliminary step, be 200m by Degussa (Germany) with the BET specific surface area that trade(brand)name Aerosil 200 sells with 44mg
2The silicon-dioxide of/g is 10
-2Under the absolute pressure of Pa in 700 ℃ of processed 15 hours so that like this silicon-dioxide of handling in infrared spectra in 3747cm
-1An absorption band occurs, this is the feature of remaining (SiO-H) key particularly.
In the first step, isolate the silicon-dioxide that 44mg prepares previously, and under argon atmospher, introduce in the glass reactor at 25 ℃.In this reactor, introduce used precursor Pr among the embodiment 1 then with general formula (3).Reactor is heated to 70 ℃ then and reaches 2 hours, so that precursor Pr is sublimate on the silicon-dioxide, and form the organo-metallic tungsten compound that is grafted on the silicon-dioxide.When finishing at this moment, by remove unreacted excessive precursor Pr at 70 ℃ of anti-sublimations.Then, with reactor cooling to 25 ℃, and isolate the organo-metallic tungsten compound that is grafted in this way on the silicon-dioxide under argon atmospher, it contains the tungsten of 5.5 weight % and has following general formula:
(Si-O)
xW[-CH
2-C(CH
3)
3]
y[≡C-C(CH
3)
3] (5)
Wherein x=1 and y=2
In second step, by contact down the organo-metallic tungsten compound that is grafted on the silicon-dioxide that the preceding step was prepared in 15 hours and carry out the hydrogenolysis processing with 150 ℃ with hydrogen at the 73kPa hydrogen pressure.When finishing at this moment, obtained compound (W/Si-1) as a comparison, and separated in argon atmospher, it comprises the tungsten hydride that is grafted on the silicon-dioxide, and contains the tungsten of 5.5 weight %; It at infrared spectra in 1940cm
-1An absorption band is arranged, and this is the feature that is grafted on (W-H) key on the silicon-dioxide especially.
Embodiment 5 (Comparative Examples): preparation is grafted on the hydrogenated tantal on the aluminum oxide
Carry out the 2 identical steps with embodiment, different is to isolate the aluminum oxide that 50mg prepares in preliminary step in the first step, and introduces the inferior neo-pentyl tantalum of three (neo-pentyls) with following general formula replace precursor Pr as precursor Pr ' in reactor:
Ta[-CH
2-C(CH
3)
3]
3[＝CH-C(CH
3)
3] (6)
Obtained to be grafted on the organo-metallic tantalum compound on the aluminum oxide thus, it contains the tantalum of 5.6 weight %.
Second step is according to carrying out with embodiment 2 identical modes, the step preparation is grafted on organo-metallic tantalum compound on the aluminum oxide before different being to use. obtained (Ta/Al-1) compound thus as a comparison, it comprises the hydrogenated tantal that is grafted on the aluminum oxide, and contains the tantalum of 5.6 weight %. it in infrared spectra in 1830cm
-1Have an absorption band, this is the feature that is grafted on (Ta-H) key on the aluminum oxide, also at 1914cm
-1Have another absorption band, this is the feature of (Al-H) key particularly.
Embodiment 6 (Comparative Examples): preparation is grafted on the hydrogenated tantal on the silicon-dioxide
Carry out the 4 identical steps with embodiment, different is to isolate the aluminum oxide that 50mg prepares in preliminary step in the first step, and introduces the inferior neo-pentyl tantalum of three (neo-pentyls) of general formula (6) replace precursor Pr as precursor Pr ' in reactor.Obtained to be grafted on the organo-metallic tantalum compound on the silicon-dioxide thus, it contains the tantalum of 5.5 weight %.
Second step is according to carrying out with embodiment 4 identical modes, and the step preparation is grafted on organo-metallic tantalum compound on the silicon-dioxide before different being to use.Obtained (Ta/Si-1) compound thus as a comparison, it comprises the hydrogenated tantal that is grafted on the silicon-dioxide, and contains the tantalum of 5.5 weight %.It in infrared spectra in 1830cm
-1Have an absorption band, this is the feature that is grafted on (Ta-H) key on the silicon-dioxide.
Embodiment 7: the replacement(metathesis)reaction of propane
In the propane replacement(metathesis)reaction of available following The Representation Equation, use respectively in embodiment 3,4,5 and 6 (W/Al-H), (W/Si-1) of preparation, (Ta/Al-1) and (Ta/Si-1) metallic compound of load successively:
2C
3H
8→C
2H
6+C
4H
10 (7)
Each propane replacement(metathesis)reaction is carried out under the following conditions." scene " prepares the metallic compound of load in glass reactor as mentioned above.Then, the reactor of finding time adds propane and reaches 76kPa until pressure, and is heated to 150 ℃.Can be observed generation and mainly comprise ethane and normal butane and Trimethylmethane and a small amount of methane, Skellysolve A and iso-pentane even minute quantity C
6The mixture of homologue.
Each experiment of carrying out for organometallic compound with load, measure and calculate every mole in the loaded metal compound tungsten and tantalum on the mole number cumulative number (CN) in time of the propane that transforms, this is to carry out when 120 hours reaction finishes.
In addition, for each experiment, when finishing in 120 hours, measure and calculate the selectivity (SnC of the reaction that generates normal butane
4) with the selectivity (SiC of the reaction that generates Trimethylmethane
4) the ratio.Selectivity (SnC
4) and (SiC
4) calculate according to following formula respectively:
(8) SnC
4=(mole number of the normal butane of generation)/(total mole number of the alkane of generation) reaches
(9) SiC
4=(mole number of the Trimethylmethane of generation)/(total mole number of the alkane of generation)
Table 1 has gathered the above-mentioned measurements and calculations result of each propane replacement(metathesis)reaction experiment of carrying out.
Table 1
| Experiment | The loaded metal compound | CN | Sn C 4/SiC 4 |
| 1 | W/Al-3 | 180 | 10 |
| 2 (contrasts) | W/Si-1 | 10 | 12 |
| 3 (contrasts) | Ta/Al-1 | 39 | 7 |
| 4 (contrasts) | Ta/Si-1 | 60 | 2.7 |
The result of analytical table 1 as seen, loaded metal compound W/Al-3 of the present invention has catalytic activity high, that be much higher than other compound in the replacement(metathesis)reaction of propane, and the normal butane that generates and the ratio of the selectivity between the Trimethylmethane have bigger value.
Embodiment 8: " methane decomposition " of propane
Make per 10
6The mixture that mole of methane contains 800 moles of propane is depressed with the flow velocity of 1.5 ml/min at the methane branch of 5MPa and is 5mL, is heated to 250 ℃ and contain the reactor of 300mg by the loaded metal compound of the present invention (W/Al-3) of embodiment 3 preparations by capacity continuously.
" methane decomposition " reaction of propane can be write as following equation:
CH
4+C
3H
8→2C
2H
6 (10)
Really can be observed and generated ethane through after a while.
Claims (14)
1. the metallic compound of a load, it comprises the carrier based on aluminum oxide, is grafted with tungsten hydride on this carrier.
2. according to the compound of claim 1, it is characterized in that described carrier is selected from and has based on the carrier of the even composition of aluminum oxide and the inhomogeneous carrier based on aluminum oxide that comprises aluminum oxide on the surface of described carrier.
3. according to each compound of claim 1 to 2, it is characterized in that described carrier comprises the aluminum oxide of aluminum oxide, blended aluminum oxide or modification.
4. according to the compound of claim 3, it is characterized in that described carrier comprises the aluminum oxide that is selected from porous alumina, non-porous aluminas and mesoporous aluminas.
5. according to the compound of claim 4, it is characterized in that described porous alumina is selected from gama-alumina, η-aluminum oxide, δ-aluminum oxide, θ-aluminum oxide, κ-aluminum oxide, ρ-aluminum oxide and χ-aluminum oxide, and described non-porous aluminas is an Alpha-alumina.
6. according to each compound of claim 1 to 5, it is characterized in that the oxidation state of tungsten has 2 to 6 value.
7. according to the compound of claim 6, it is characterized in that the oxidation state of tungsten has 4 to 6 value.
8. according to each compound of claim 1 to 5, it is characterized in that tungsten atom is connected with one or more hydrogen atoms, and randomly be connected with one or more alkyl R.
9. according to each compound of claim 1 to 5, it is characterized in that tungsten atom and one or more hydrocarbon part complexings.
10. according to the compound of claim 9, it is characterized in that tungsten atom and aromatic ligand complexing.
11., it is characterized in that tungsten atom and carbonyl ligands complexing according to each compound of claim 1 to 5.
12. according to each compound of claim 1 to 11 as the purposes of the catalyzer of the replacement(metathesis)reaction of hydrocarbon.
13. according to the purposes of claim 12, described hydrocarbon is an alkane.
14. according to the purposes of claim 13, described alkane is propane.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR0303588A FR2852866B1 (en) | 2003-03-25 | 2003-03-25 | SUPPORTED METAL COMPOUND, PROCESS FOR PREPARING AND USE OF THE COMPOUND IN HYDROCARBON METATHESIS REACTIONS |
| FR03/03588 | 2003-03-25 | ||
| PCT/FR2004/000730 WO2004089541A2 (en) | 2003-03-25 | 2004-03-24 | Metallic compound fixed to a support, method for production and use of said compound in hydrocarbon metathesis reactions |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1795153A CN1795153A (en) | 2006-06-28 |
| CN1795153B true CN1795153B (en) | 2010-05-05 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2004800145147A Expired - Fee Related CN1795153B (en) | 2003-03-25 | 2004-03-24 | Metallic compound fixed to a support, method for production and use of said compound in hydrocarbon metathesis reactions |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US20070129584A1 (en) |
| EP (1) | EP1603852A2 (en) |
| CN (1) | CN1795153B (en) |
| FR (1) | FR2852866B1 (en) |
| WO (1) | WO2004089541A2 (en) |
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| US7838708B2 (en) | 2001-06-20 | 2010-11-23 | Grt, Inc. | Hydrocarbon conversion process improvements |
| US20050171393A1 (en) | 2003-07-15 | 2005-08-04 | Lorkovic Ivan M. | Hydrocarbon synthesis |
| CA2532367C (en) | 2003-07-15 | 2013-04-23 | Grt, Inc. | Hydrocarbon synthesis |
| US8173851B2 (en) | 2004-04-16 | 2012-05-08 | Marathon Gtf Technology, Ltd. | Processes for converting gaseous alkanes to liquid hydrocarbons |
| US20080275284A1 (en) | 2004-04-16 | 2008-11-06 | Marathon Oil Company | Process for converting gaseous alkanes to liquid hydrocarbons |
| US20060100469A1 (en) | 2004-04-16 | 2006-05-11 | Waycuilis John J | Process for converting gaseous alkanes to olefins and liquid hydrocarbons |
| US7244867B2 (en) | 2004-04-16 | 2007-07-17 | Marathon Oil Company | Process for converting gaseous alkanes to liquid hydrocarbons |
| US8642822B2 (en) | 2004-04-16 | 2014-02-04 | Marathon Gtf Technology, Ltd. | Processes for converting gaseous alkanes to liquid hydrocarbons using microchannel reactor |
| US7674941B2 (en) | 2004-04-16 | 2010-03-09 | Marathon Gtf Technology, Ltd. | Processes for converting gaseous alkanes to liquid hydrocarbons |
| BRPI0707490A2 (en) | 2006-02-03 | 2011-05-03 | Grt Inc | halogen light gas separation |
| EP2457887A1 (en) | 2006-02-03 | 2012-05-30 | GRT, Inc. | Continuous process for converting natural gas to liquid hydrocarbons |
| CN101479216A (en) * | 2006-06-26 | 2009-07-08 | 英国石油国际有限公司 | Process for preparing 2, 3-dimethylbutane and uses of the resulting products |
| KR20100027141A (en) | 2007-05-24 | 2010-03-10 | 지알티, 인코포레이티드 | Zone reactor incorporating reversible hydrogen halide capture and release |
| EP2045013A1 (en) | 2007-10-03 | 2009-04-08 | Bp Oil International Limited | Solid metal compound, preparations and uses thereof |
| EP2103586A1 (en) * | 2008-03-20 | 2009-09-23 | Bp Oil International Limited | Process for converting methane into ethane in a membrane reactor |
| US8282810B2 (en) | 2008-06-13 | 2012-10-09 | Marathon Gtf Technology, Ltd. | Bromine-based method and system for converting gaseous alkanes to liquid hydrocarbons using electrolysis for bromine recovery |
| AU2009270801B2 (en) | 2008-07-18 | 2014-04-24 | Reaction 35, Llc | Continuous process for converting natural gas to liquid hydrocarbons |
| US8198495B2 (en) | 2010-03-02 | 2012-06-12 | Marathon Gtf Technology, Ltd. | Processes and systems for the staged synthesis of alkyl bromides |
| US8367884B2 (en) | 2010-03-02 | 2013-02-05 | Marathon Gtf Technology, Ltd. | Processes and systems for the staged synthesis of alkyl bromides |
| US8389788B2 (en) | 2010-03-30 | 2013-03-05 | Uop Llc | Olefin metathesis reactant ratios used with tungsten hydride catalysts |
| US8704029B2 (en) * | 2010-03-30 | 2014-04-22 | Uop Llc | Conversion of butylene to propylene under olefin metathesis conditions |
| US8815050B2 (en) | 2011-03-22 | 2014-08-26 | Marathon Gtf Technology, Ltd. | Processes and systems for drying liquid bromine |
| US8436220B2 (en) | 2011-06-10 | 2013-05-07 | Marathon Gtf Technology, Ltd. | Processes and systems for demethanization of brominated hydrocarbons |
| US8829256B2 (en) | 2011-06-30 | 2014-09-09 | Gtc Technology Us, Llc | Processes and systems for fractionation of brominated hydrocarbons in the conversion of natural gas to liquid hydrocarbons |
| US8802908B2 (en) | 2011-10-21 | 2014-08-12 | Marathon Gtf Technology, Ltd. | Processes and systems for separate, parallel methane and higher alkanes' bromination |
| US9193641B2 (en) | 2011-12-16 | 2015-11-24 | Gtc Technology Us, Llc | Processes and systems for conversion of alkyl bromides to higher molecular weight hydrocarbons in circulating catalyst reactor-regenerator systems |
| EP2918546A4 (en) * | 2012-11-06 | 2016-06-29 | Kawai Lime Industry Co Ltd | High thermal conductive boehmite and method for manufacturing same |
| EP2786978B1 (en) * | 2013-04-03 | 2016-12-07 | Scg Chemicals Co. Ltd. | Process for converting paraffin to olefin and catalyst for use therein |
| EP2985077A1 (en) | 2014-08-11 | 2016-02-17 | PFW Aroma Chemicals B.V. | Supported molybdenum or tungsten complexes, its preparation and use in olefin metathesis |
| US10308572B2 (en) | 2015-06-25 | 2019-06-04 | King Abdullah University Of Science And Technology | Process for compound transformation |
| EP3500523A1 (en) * | 2016-08-17 | 2019-06-26 | SABIC Global Technologies B.V. | Heterogeneous catalysts/process based on supported/grafted transition metal hydrides for ammonia formation from nitrogen and hydrogen |
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| FR2872510B1 (en) * | 2004-07-02 | 2006-09-08 | Cpe Lyon Fcr | PROCESS FOR TRANSFORMING ETHYLENE TO PROPYLENE |
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- 2003-03-25 FR FR0303588A patent/FR2852866B1/en not_active Expired - Fee Related
-
2004
- 2004-03-24 EP EP04742338A patent/EP1603852A2/en not_active Withdrawn
- 2004-03-24 CN CN2004800145147A patent/CN1795153B/en not_active Expired - Fee Related
- 2004-03-24 US US10/550,628 patent/US20070129584A1/en not_active Abandoned
- 2004-03-24 WO PCT/FR2004/000730 patent/WO2004089541A2/en active Application Filing
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| US6229060B1 (en) * | 1996-07-12 | 2001-05-08 | Centre National De La Recherche Scientifique (C.N.R.S.) | Method of metathesis of alkanes and catalyst |
| CN1372534A (en) * | 1999-07-09 | 2002-10-02 | 英国石油化学品有限公司 | Process for manufacturing alkanes with methane |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2004089541A2 (en) | 2004-10-21 |
| EP1603852A2 (en) | 2005-12-14 |
| WO2004089541A3 (en) | 2004-11-18 |
| US20070129584A1 (en) | 2007-06-07 |
| FR2852866B1 (en) | 2006-07-14 |
| FR2852866A1 (en) | 2004-10-01 |
| CN1795153A (en) | 2006-06-28 |
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